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Statistical Thermodynamics Chapter 16

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Ideal Gases 1L =1 dm 3 = 0.001 m 3 1L=1000 cm 3 , cc, mL 1m 3 =1000 dm 3 =10 6 cm 3 RT V P nRT PV 1 Chapter 16: The Properties of Gases
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Page 1: Statistical Thermodynamics Chapter 16

Ideal Gases

1L =1 dm3= 0.001 m3

1L=1000 cm3, cc, mL 1m3 =1000 dm3 =106 cm3

RTVPnRTPV

1

Chapter 16: The Properties of Gases

Page 2: Statistical Thermodynamics Chapter 16

Gas Constant

2

Page 3: Statistical Thermodynamics Chapter 16

Real Gases versus Ideal Gases

3

300 K

CH4

Page 4: Statistical Thermodynamics Chapter 16

Van der Waals, Redlich-Kwong, Peng-Robinson

4

Page 5: Statistical Thermodynamics Chapter 16

5

Page 6: Statistical Thermodynamics Chapter 16

6

Page 7: Statistical Thermodynamics Chapter 16

Van der Waals, Redlich-Kwong, Peng-Robinson

vdw ??

ethane at 400 K

ethane at 305.33 K

7

Page 8: Statistical Thermodynamics Chapter 16

Experimental P-V isotherms of CO2

8

Page 9: Statistical Thermodynamics Chapter 16

Cubic Equations of State describe both liquid and gaseous region

9

Page 10: Statistical Thermodynamics Chapter 16

Critical values of Pc , Vc , and Tc for vwd EOS

Critical values of Pc , Vc , and Tc for R-K EOS

10

27

8 27

3 2 bRaT

baPbV ccc

Page 11: Statistical Thermodynamics Chapter 16

The value of is constant !!

11

Page 12: Statistical Thermodynamics Chapter 16

The constant values of EOS can be obtained from Pc and Tc

12

Page 13: Statistical Thermodynamics Chapter 16

Law of Corresponding States (LOCS)

13

Page 14: Statistical Thermodynamics Chapter 16

Based on LOCS, all gases have the same functional

14

Page 15: Statistical Thermodynamics Chapter 16

Virial Equation of State

15

Page 16: Statistical Thermodynamics Chapter 16

Experimental Determination of B2V

B2V and Temperature

16

Page 17: Statistical Thermodynamics Chapter 16

Relationships between virial coefficients and intermolecular interactions

r

Lennard-Jones Potential

17

Page 18: Statistical Thermodynamics Chapter 16

18

Page 19: Statistical Thermodynamics Chapter 16

Divide both sides by

B2V and LOCS

19

xr/TkT B VH /*

Page 20: Statistical Thermodynamics Chapter 16

@ T* | 3.2 , B2v (T*) =0

B*2V vs T* and Boyle Temperature

20

Page 21: Statistical Thermodynamics Chapter 16

The second virial coefficient indicates the first deviation from ideal gas

21

Page 22: Statistical Thermodynamics Chapter 16

Three contributions to attractive force

22

Page 23: Statistical Thermodynamics Chapter 16

Hard-Sphere Potential

23

Page 24: Statistical Thermodynamics Chapter 16

Square-Well Potential

24

Page 25: Statistical Thermodynamics Chapter 16

Relationship between B2V and a, b coefficients in vdw EOS

25

Page 26: Statistical Thermodynamics Chapter 16

Relationship between B2V and a, b coefficients in vdw EOS

drreNdrrNTB 2rTkc

A2

A6

B ]1[2 )1(2- )(

0v2

6

³³f

��� V

V

SS 1 / 66 ¢¢rTkc B

36

2

3 2

VS cNa A

32 3

ANb SV

26

"��� 2!xxe2

x 1


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